Color photographic material

ABSTRACT

WHEREIN X is hydrogen, halogen, a lower alkoxy group, a lower alkyl group or an aryloxy group; and Y is   D R A W I N G WHERE R1 is a lower alkyl group; R2 is a hydrocarbon residue having eight to 18 carbon atoms; and COR3 is an acyl group having nine to 20 carbon atoms. A yellow color image-forming coupler, useful as a protect type coupler in a light-sensitive silver halide color photographic emulsion. The coupler has the general formula

United States Patent [191 Inoue et a].

[111 3,832,386 Aug. 27, 1974 [73] Assignee: Kanishiroku Photo Industry Co.,

Ltd.

22 Filed: May 13, 1971 21 Appl. No.: 143,241

[30] Foreign Application Priority Data May 14, 1970 Japan 45-40492 [52] US. Cl 260/471 R, 96/100, 260/326.3,

260/404.5, 260/558 R, 260/559 R [51] Int. Cl. C07c 103/30 [58] Field of Search 260/471 R, 404.5

[56] References Cited UNITED STATES PATENTS 3,644,498 2/1972 Loria 260/471 R Primary ExaminerLorraine A. Weinberger Assistant E.\'aminerL. A. Thaxton Attorney, Agent, or FirmWaters, Roditi, Schwartz & Nissen [57] ABSTRACT A yellow color image-forming coupler, useful as a protect type coupler in a light-sensitive silver halide color photographic emulsion. The coupler has the general formula I X I (camcQ-c oomooNHQ wherein X is hydrogen, halogen, a lower alkoxy group, a lower alkyl group or an aryloxy group; and Y is where R is a lower alkyl group; R is a hydrocarbon residue having eight to 18 carbon atoms; and COR is an acyl group having nine to 20 carbon atoms.

2 Claims, No Drawings -GOOElH-COORz, COOR2, N

COLOR PHOTOGRAPHIC MATERIAL This invention relates to a light-sensitive color photographic material. More particularly, the invention pertains to a color photographic material containing a yellow color image-forming novel coupler belonging to the so-called protect type coupler. i.e., a waterinsoluble or difficulty water-soluble coupler to be used by dissolving the same in a difficulty water-miscible 1 high boiling solvent and dispersing the resulting solution in a photographic emulsion. The novel yellow coupler is represented by the general formula,

wherein X is hydrogen, halogen, a lower alkoxy group, a lower alkyl group or an aryloxy group; and Y is a group of the formula,

CO-GH-Rz or NHCOR:

( mnoQ-ooomo ONHQ where R, is a lower alkyl group; R is a hydrocarbon residue having eight to 18 carbon atoms; and COR- is an acyl group having nine to 20 carbon atoms.

(CHzhO-GCOCHzCONH-Q Heretofore, many compounds have been proposed as protect type yellow couplers. However, they have various drawbacks in spectral absorption characteristic, light and moisture fastness of the resulting images. and

i so those which have satisfactory characteristics are not many.

(CHa)aC @oocmc ONH nncooHmGtonm (came-Go ocmc ONH- In contrast thereto, the coupler of the aforesaid general formula, which is used in the present invention, has a t-butyl group substituted in the p-position of the benzoyl portion, so that it can overcome the abovementioned drawbacks of the conventional couplers and gives such effects that the resulting color image becomes unexpectedly excellent in color reproduction and comes to be improved in stability as well. These effects are considered to be ascribable to the branched tertiary alkyl group in the p-position. Further, the coupler is easily soluble in such a high boiling solvent as di butyl phthalate or tricresyl phosphate, so that the amount of solvent for the coupler can be decreased to give a high concentration dispersion, which is difficultly crystallized in a photographic emulsion or a film formed by coating and drying the emulsion. Thus, the

coupler of the present invention has greatly overcome the drawbacks of the conventional couplers.

Typicalexamples of the compound of the aforesaid 20 general formula are set forth below, but couplers usable in the present invention are not limited only to these.

6611? WWW o 0-0 Hz a-(4-t-Butylbenzoyl)-2-methoity-5- I octadecylsuccinimide acetanilide C O OCH-C O O CnHss a-(4 tButylbenzoyl)-2-chloro-5-(b4- dodecyloxycarbonyl ethoxycarbonyl) acetanilide I a-(4-t-l3utylbenzoyl)-2-pl1enoxy-5 dodecyloxycarbonyl acetanilide NH0 0 0 Hi1 a-(4-t-Butylbenzoyl)-2-methyl ;myristarnide 555 i: anilide halal-In tCsHn with metallic sodium in benzene. Thereafter. the reaction product was deacetylated by boiling in sodium alcoholate. poured into water, and then acidified with hydrochloric acid to deposit an oily substance. This'oily substance was extracted with ether, and the ether layer was concentrated and subjected to distillation to obtain a fraction of l42l45C/ 3 mm in a yield of 63 percent.

ii. The thus obtained 4-tbutylbenzoylacetic acid ethyl ester was condensed in xylene with an amine component. That is, 12.4 g. of the keto-acid ester obtained in the above step (i), 22.8 g. of 2-methoxy-5- octadecyl succinimide aniline (m.p. 8788C.) and 70 ml. of xylene were mixed together, and the resulting mixture was boiled. After removing the formed alcohol by distillation, the mixture was refluxed for 3 hours. Thereafter, the xylene was removed by distillation, and the residue was thoroughly stirred with .hexane to deposit a precipitate. Subsequently, the precipitate was recovered by filtration, dried and then recrystallized from methanol to obtain g. of a white powder, m.p. 707lC., yield 74 percent. This powder was the exemplified coupler l.

in the same manner asv above,the exemplified coupler 2 was obtained from 2-chloro-5-(adodecyloxycarbonyl ethoxycarbonyl) aniline; the exemplified coupler v 3 from 2-phenoxy-5- dodecyloxycarbonyl aniline; the exemplified coupler 4 from 2-methyl-5-myristarnidoaniline; the exemplified coupler 5 from 2-chloro-5-(2,4-di-tertamylphenoxyacetamide) aniline; the exemplified .coupler 6 from 3-(2,4,6-tri-sec-butylphenoxyacetamide) aniline; the exemplified coupler 7 from 2-ethoxy-5-(adi-tert-amylphenoxybutylamide) aniline; the exempli- Table l Excmplificd Melting Nitrogen analysis $7: I

point coupler 1 (C) Cald Found 4 I20 l25 5.24 5.l6

7 ll6- ll7 4.27 4.l6

10 ll() ll2 3.93 3.88

ll 132 I34 4.57 4.53

Test results showing the fact that the color images of color photographic materials containing the couplers 1,

2 and 5 of the present invention are excellent in spectral absorption characteristic are set forth in Table 2.

' In the table, the present invention couplers are compared in spectral absorption characteristic of the resulting color images with known couplers, and the value (m;t) is the absorption wave length at an optical density (D) of 0.2, the value of Amax(mp.) is the absorption maximum wave length at an optical density of 1.0,

and the value of AMmp.) is the difference between the said two values. AMm) A, Amax 'TA'BLE? Amax(D==1.0) arm-0.2) Coupler (mu) (mu) M u) Known coupler.

Y 01H: 447 aao 8s tCiHnQ-O (EH-C 0NH- 0cm t H ooHio ONH-- Known coupler I 1 NHo0oH5o-toim1 tCsHn I Exempllfied coupler 1 445 514 69 Exempllfied coupler 2... 452 520 68 452 521 69 Exemplified coupler 3-..

From Table 2, it is understood that the couplers of the present invention are excellent in absorption characteristic of color images.

In the next place, test results showing the fact that the of to 100 g. per mole of silver halide, but may be varied so as to be in conformity to application purposes, without being limited to the above-mentioned range. Further, it is not objectionable to add the coucolor images of photographic materials containing the pler of the present invention to 2 or more of emulsion couplers l, 2 and 3 of the present invention are excellayers of a multi-layered color photographic material. lent in stability are set forth in Table 3, in which the numerals percentages of residual color density. The emulsion used inthe present invention may be 'rABLi'I's T Fading resistance (irra- Moisture resistance (allowdiation with are lamp ing to stand at 50 C. Coupler for 16 hours) 80% RH for 14 days) Known coupler (1,11, 83 96 tCsHnQ-OCHCONH OCH:

tCsHn ooomoonn Known coupler (31 83 97 HzCO-COCT12CONH NHCOCHzOQ-Kldln Exemplified coupler 1 86 98 Exemplified coupler 2 85 98 Exemplified coupler 5 87 99 The test results set forth in Tables 2 and 3 are measured values of color images formed by developing the individual photographic materials with N-ethyl-N-B methanesulfonamidoethyl-3-methyl-4-aniline according to Example 1 shown later.

As is clear from Tables 2 and 3, it is understood that the couplers of the present invention are excellent in spectral absorption characteristic and stability of color images as compared with the case of the known couplers, and hence are quite excellent as protect type couplers.

For the incorporation of the couplers of the present invention into a light-sensitive color photographic material, there may be adopted any of the known procedures. For example, the coupler, or a mixture of the couplers, of the present invention is dissolved in a high boiling solvent (b.p. 175C. or more) such as tricresyl phosphate or dibutyl phthalate, or in a low boiling solvent such as butyl acetate or butyl propionate, or a mixture of said solvents. This solution is mixed with an aqueous gelatine solution containing a surface active agent, and then emulsified by means of a high speed rotary mixer of a colloid mill to form a dispersion. The

thus formed dispersion is directly added to a silver halide photographic emulsion, which is then coated on a support such as glassplate, synthetic resin sheet, resin film base, baryta paper or laminated paper, followed by drying, to prepare a light-sensitive color photographic ln th e above case, the

amount of coupler to be added to the photographic emulsion is preferably in the range N-hydroxyethyl-Z-methyl-p-phenylenediamine,

prepared by use of any of such silver halides as silver chloride, silver iodobromide and silver chlorobromide, and may contain a chemical sensitizer, e.g., sulfur sensitizer, a natural sensitizer present in gelatine, a reducing sensitizer or a noble metal salt. Further, the emulsion may have been incorporated with any of ordinary photographic additives such as, for example, antifoggant, stabilizers, anti-stain agents, anti-irradiation agents, physical property-improving high molecular additives, hardeners and coating aids. Still further, the emulsion may contain a known carbocyanine or merocyanine dye as an optical sensitizer therefor.

The thus obtained light-sensitive color photographic material of the present invention is exposed to radioactive rays such as a-rays or B-rays, visible rays or infrared rays, developed with a developer containing a pphenylenediamine type developing agent as a main ingredient, and then bleached, desilvered and fixed to obtain a high density color image which is excellent in spectral absorption characteristic and durability and high in transparency. Further, a color photographic material containing the coupler of the present invention is incorporated with an UV-absorber of the benzephenone type (e.g. 2-hydroxy-4- dodecyloxybenzophenone) or the triazole type [e.g., 2-( 2-hydroxy-3 ,5 '.-di-tert-butylphenyl) benzotriazole], whereby the resulting color image can further be increased in durability.

Typical examples of the main ingredient of the developer used for development of the present color photographic material are sulfates, sulfites and hydrochlorides of N,N-diethyl-p-phenylenediamine, N-ethyl-N-B- methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl- N,N- diethyl-2-methyl-p-phenylenediamine and N,N-diethyl- Z-methyl-p-phenylenediamine. Further, the developer may contain a development-controlling agent such as citrazinic acid, in addition to the above-mentioned main ingredient.

9 The present invention is'illustrated further detail below with reference to exainples, but it is needless to say that the examples are illustrative and the invention is not limited only to these. Example 1 20.0 Grams of the exemplified to a mixed solution comprising 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate, and the resulting mixture was heated to 60C., whereby the coupler was completely dissolved. The thus formed solution was Alkanol B v(alltylriaphthalenesulfonate, produced by Du Font and 200'rnl..of a Spercent aqueous gelatine coupler l was added The thus prepared photographic material was exposed and then developed at 21C. for 12 minutes with r a developer of the following composition:

' mixed with 10 ml. of a 10 percentaqueous solution of solution, and the mixture was subjected to a colloid mill N-Ethyl- N flmcthanesulfonamidocthyl-Iimethyl-4-aminoanilinc sulfate 5.0 g. Anhydrous sodium sulfite 2.0 g. Benzyl alcohol 3.8 g. Sodium carbonate (monohydrate) 50.0 g. Potassium bromide 1.0 g. Caustic soda 0.55 g. Water to make 1,000 ml.

Thereafter, the developed material was subjected to ordinary stopping and fixing treatments, washed with water for 10 to 15 minutes and then treated for 5 mintion:

I00 g. 50 g. L000 ml.

Potassium ferricyanidc Potassium bromide I Watcr to make Subsequently, the material was washed with water'for utes with a bleaching solution of the following composi- 5 minutes and then fixed for 5 minutes in a fixing bath of the following composition:

Sodium thiosulfate 250 g.- Water to make 1.000 ml.

Thereafter, the thus treated material was washed with water for 20 to 25 minutes and then dried to obtain a 7 clear yellow color image having an absorption maximum at 445mg. Example 2 l0 Grams of the exemplified coupler (2) was added to a mixed solution comprising 10 ml. of tricresyl phosphate and 30 ml. of butyl acetate, and the resulting mixture was heated to 50C., whereby the coupler was completely dissolved. The thus formed solution was mixed with 5 ml. of a 10 percent aqueous Alkanol B solution and 800 ml. of a 5 percent aqueous gelatine solution, and the mixture was subjected to a colloid mill to form a dispersion. This coupler dispersion was added to 500 g. of a gelatine silver iodobromide emulsion, which was then coated on a polyester film base and then dried coating film. g Y

p-Methylaminophenyl sulfate 3.0 g. Anhydrous sodium sulfite lit-. 50.0 g. Hydroquinone 6.0 g. Anhydrous sodium carbonate I 40.0 g. Potassium bromide v, 3.5 g. Potassium rhodanide- 2.0 g. Water to make I 1,000 ml.

After ordinary stopping, film-hardening and waterwashing treatments, the material .was subjected to'sec-. ond exposure by use of a white ligh t gand then developed at 21C; for 3 minutes with adeyelo'per of the following composition: i "1 I N,N-Diethyl2-mcthyl-p-phenylcnediamine Anhydrous sodium sulfite 5 Sodium carbonate (monohydrate) Potassium bromide Water to make Subsequently, the thus treated material'was j to ordinary stopping, water-washing, bleachingandi fix ing treatments, washed with running water for 20 n1 utes and then dried to obtain a yellow positive color image which had an absorption maximum at 455 mp.

and was excellent in transparency. Example 3 l0 Grams of the exemplified coupler (3) was added to 20 ml. of dibutyl phthalate, and the resulting mixture was heated 'to 50C., whereby the coupler was completely dissolved. The thus formed solution was mixed with 5 ml. of a 10 percent aqueousAlkanol B solution. and 200 ml. of a 5 percent aqueous gelatine. solution,

and the mixture was subjected several times to a colloid mill to form a dispersion. This dispersion was added to 500 g. of a gelatine silver chlorobromide emulsion,

which was then coated on a'baryta paper; followed by drying, to prepare;alight-sensitive material. The thus prepared light-sensitive-material was exposed and then developed at 25C. for l0jminutes in a bath having the following composition:

. N Ethyl-N-23-mcthanesulfonamidocthyl-3- Thedevelopedmaterial was dipped for 2 to 4 minutes in a stopping-fixing bath of the following composition:

Ammonium thiosulfate I g. Potassium metabisulfite 20 g. Glacial acetic acid 10 cc. Water to .make 1000 ml.

Subsequently, the material with water for 5 minutes and then bleached at 25C. for 3 minutes in a bath of the following composition:

" Water to make 3 l Sodium nitrate 28.0 g. Potassium ferricyanidc l0.0 g. ,Boric acid 7.5 g,v Potassium bromide 7.5 g, 000 ml,

Thereafter, the material was washed with water for minutes, dipped in a stabilization bath for 2 minutes and then dried to obtain a yellow color image which What we claim is: r l.-A compound selected from the group consisting of wherein X is hydrogen, halogen, a lower alkoxy group,

a lower alkyl group ora phenoxy group; and Y is where R is a lower alkyl grou ariiifigigfiydibcibon' had an absorption maximum at 445 my. and was excel- I lent, in resistance to light and moisture. i i

residue having eight to 18 carbon atoms.

2. A compound as claimed in claim 1, having the formula A j g 

2. A compound as claimed in claim 1, having the formula 